JPH04122429A - Dispersion stabilizer of organic powder - Google Patents

Abstract

PURPOSE:To disperse an organic powder stably in water or an oil with a high concentration and low viscosity for a long duration by using a copolymer of a specified polyoxyalkylene derivative and maleic acids. CONSTITUTION:A dispersion stabilizer for an organic powder is obtained from copolymer of polyoxyalkylene derivative with maleic anhydride, maleic acid, maleic acid salts, or maleic acid esters shown as a formula I (Z stands for a compound residue having 2-8 hydroxy groups, AO stands for a 2-16C oxyalkylene, R<1> stands for a 2-5C unsaturated hydrocarbon group, R<2> stands for a 1-4C hydrocarbon group or acyl, (a)=0-1000, (b)=0-1000, (c)=0-1000, (al+bm+cn)=1-3000, (l)=1-8, (m)=0-2, (n)=0-7, (l+m+n)=2-8, (m)/(l+n)<=1/3).

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention provides a dispersion stabilization method for stably dispersing various organic powders such as organic pigments, metal soaps, and synthetic resin powders in water and in 4 (1) at high concentrations. Regarding drugs.

[Conventional technology]

Organic powders are used in various industrial fields by being dispersed in water, water, etc. Examples include organic pigments for paints and inks, synthetic resin powders, and metal soaps used as lubricants for papermaking. Organic powders often have insufficient dispersibility when used alone, and conventionally, many polymeric surfactants such as polyacrylic acid, salts of these copolymers, maleic anhydride and α-olefins have been used as dispersion stabilizers. copolymer of '
jJF+ etc. have been proposed.

[Problem to be solved by the invention]

However, with conventional dispersion stabilizers, it has been difficult to disperse 41 powder at a high concentration and low viscosity that can be applied to various fields.

The object of the present invention is to provide a dispersion stabilizer capable of manually dispersing organic powders in water and oil at high concentrations and low viscosity over long periods of time.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the inventors found that a copolymer of a specific polyoxyalkylene derivative exhibits excellent performance as a dispersion stabilizer for various organic powders in water and in oil. This discovery led to the completion of this invention.

That is, the present invention provides an organic powder comprising a copolymer of a polyoxyalkylene derivative represented by the formula (]) and maleic anhydride, maleic acid, a maleate salt, or a maleic acid ester (hereinafter collectively referred to as maleic acids). It is a dispersion stabilizer.

[○(A○)aR1koQ / Z-[○(A○)bHcom (
1)\[○(A○)cR”]n (However, 2 is l of a compound having 2 to 8 hydroxyl groups, A
○ is an oxyalkylene group having 2 to 18 carbon atoms, R1 is an unsaturated hydrocarbon group having 2 to 5 carbon atoms, R2 is a hydrocarbon group or acyl group having 1 to 40 carbon atoms, a = O-1000, b
=o-1000, c0-1000. a%+bm+cn=
1-3000, Q=1-8, m=O-2, n=
O-7teQ +mten = 2-8, m/(Q-1-n
)≦1/3. ) 2 to 8 where 2 in formula (1) is a residue
Compounds with hydroxyl groups include polyhydric phenols such as catechol, resorcinol, hydroquinone, and phloroglucin; ethylene glycol, polypyrene glycol, butylene glycol, dodecylene glycol, octadecylene gelylcol, neopentyl glycol, and styrene glycol. , glycerin, diglycerin, polyglycerin, 1~
Limethylol ethane, 1 - Limethylol propane, 1.
．． 3.5-Pentanetriol, erythritol, pentaerythrol, dipentaerythrol, sorbitol, sorbitan, sorbite, solgo-1-heru-glycerin condensate, ar-1-2-l, arabitol, chiral-1- Polyhydric alcohols such as 1-hose, mannitol; Saccharides such as melezi 1--ase; partially etherified products and partially esterified products thereof, etc.

The oxyalkylene group having 2 to 18 carbon atoms represented by A○ includes oxyethylene group, oxypropylene group, oxybutylene group, oxytetramethylene group, oxystyrene group, oxyalkylene group, oxytetramethylene group,
There are oxyhexadecylene groups, oxyoctadecylene groups, etc., and they may be adducts of one type or a mixture of two or more types, but
When there are two or more types, it may be a random adduct or a block adduct.

Examples of the unsaturated hydrocarbon group having 2 to 5 carbon atoms represented by R' include vinyl group, allyl group, methallyl group, 3-butenyl group, 4-pentenyl group, and 3-methyl-3-butenyl group.

Hydrocarbon groups having 1 to 40 carbon atoms represented by R2 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, octyl group. group, nonyl group, decyl group, 1-decyl group, iso-lysosyl group, tetradecyl group, hexadecyl group, isohexadecyl group, octadecyl group, isooctadecyl group, oleyl group, octyldodecyl group, tocosyl group, decylte)- Examples of acyl groups include rabsyl group, benzyl group, cresyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, dinonylphenyl group, styrenated phenyl group, and naphthyl group. Acetic acid, propionic acid, butyric acid, isobutyric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, isopalmitic acid, stearic acid, isostearic acid, arachidic acid, behen There are acyl groups derived from acids such as palmi-leic acid, oleic acid, linoleic acid, lylunic acid, erucic acid, and benzoic acid.

Maleates include ammonia; methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, 2-ethylhexylamine,
Monoamines such as decylamine, dodecylamine, iso-1-litecylamine, tetradecylamine, hexadecylamine, isohexadecylamine, octadecylamine, instearylamine, oleylamine, linolamine, octyl I-decylamine, tocodylamine, decyltetradecylamine, aniline, etc. ; Polyamines such as ethylenediamine, TeI-ramethylenecyamine, I-decylpropylenediamine, octadecylpropylenecyamine, oleylpropylenediamine, diethylene-1-cyamine, 1-lyethylenetetramine, TeI-diethylenepentamine, pentaethylenehexamine, etc. ; Monoethanolamine, jetanolamine, triethanolamine,
Alkanolamines such as monoisopropanolamine, diisopropanolamine, triisopropanolamine, alkyleneoxy 1-adducts of the above-mentioned monoamines and diamines; arginine, amino acids with histidine curve; lithium, sodium chloride, etc. There are salts of alkaline earth metals such as , potassium, and alkaline earth metals such as magnesium and calcium.

Maleic acid esters include methanol, ethanol, allyl alcohol, methallyl alcohol, propatool, impropatool, butanol, isobutanol,
Tert-butanol, pentanol, hexanol, 2-ethylhexanol, octatool, nonanol, decanol, dodecanol, iso-1-ridecanol, tert-radecanol, hexatecanol, isocetyl alcohol, octadecanol, isostearyl alcohol, oleyl Alcohol, alkaline such as octyldodecanol, docosanol, decylna-1-latecanol; alkylene oxide adducts of these; phenol, cresol,
There are esters of adducts of phenols such as butylphenol, octylphenol, nonylphenol, and dodecylphenol to alkyleneoxy 1.

The copolymer used in this invention can be obtained by copolymerizing the compound of formula (1) and maleic acids using a radical catalyst. Copolymers of maleic acid, maleic acid salts, or maleic esters can also be obtained by esterification, hydrolysis, and neutralization reactions of maleic anhydride copolymers.

When copolymerizing the compound of formula (1) with maleic acids, copolymerizable components such as styrene, α-olefin, isobutylene, diisobutylene, and vinyl acetate may be mixed and copolymerized; It is preferable that the amount of the compound 1) is 30 mol% or more. The equivalent ratio of the total amount of components copolymerizable with the compound of formula (1) to maleic acids is from 3 to 7:3, preferably about 1:1, based on the polymerizable double bond.

The weight average molecular weight of the copolymer is 1,000 or more, preferably 10,000 to 2,000,000.

If Q in formula (1) is 1, a linear copolymer will be obtained, and if it is 2 or more, a copolymer with a crosslinked structure will be obtained.

Regarding the relationship between Q, m and n, if m/(11+n) is larger than 173, a preferable copolymer ~9 cannot be obtained.

The copolymers used in this invention include Z, A○, R゛, R2,
The degree of hydrophilicity and lipophilicity can be changed by changing ρ, m, and n, and can be appropriately selected depending on the type of organic powder and dispersion medium.

The organic powder to be dispersed in this invention is not particularly limited, but organic pigments such as insoluble azo pigments, phthalocyan blue, dyed lake, isoindolinone, quinacridone, dioxazine violet 1-, perinone, perylene;
Synthetic resin powder such as polyamide I synthetic resin, polyester synthetic resin, polyolefin synthetic resin, polycarbonate, polyvinyl chloride, polymethyl methacrylate, fluororesin; aluminum stearate, zinc stearate, calcium stearate, magnesium stearate, Examples include metal soaps such as lead stearate, 1-mium stearate, barium stearate, calcium laurate, zinc laurate, and wood flour.

Examples of the dispersion medium in which the organic powder is dispersed using the dispersion stabilizer of the present invention include water, oil, and the like.

Oils include fuel oils such as kerosene, light oil, and heavy oil, aliphatic hydrocarbon oils such as hexane, cyclohexane, and isooctane, aromatic hydrocarbon oils such as benzene, toluene, and xylene, ethyl acetate, dioctyl phthalate, soybean oil, and linseed oil. Esterura such as oil, 1,1. ．． Examples include halogenated hydrocarbon oils such as 1-trichloroethane, 1-lychloroethylene, and chlorodifluoromethane, liquid paraffin, liquid resin for paints, and liquid rubber.

When using the dispersion stabilizer of the present invention to obtain an organic powder dispersion in water or an in-oil dispersion, the amount of the dispersion stabilizer used is 0.05 to 10 parts by weight per 00 parts by weight of the organic powder; Preferably it is 0.1 to 7 parts by weight. If the amount is less than 0.05 parts by weight, the effect will be poor, and if it is used in an amount greater than 10 parts by weight, the effect will not be significantly improved, which is economically disadvantageous.

To obtain a dispersion of organic powder in water or in oil using the dispersion stabilizer of the present invention, it is sufficient to follow the open method.
For example, a method can be employed in which an organic powder is added to water or oil containing the above-mentioned dispersion stabilizer at MN, and the mixture is stirred using a suitable stirrer.

〔Effect of the invention〕

In this invention, by using a copolymer of a specific polyoxyalkylene derivative and maleic acids as a dispersion stabilizer for organic powder, organic powder can be immersed in water or oil for a long period of time at high concentration and low viscosity. can be stably dispersed.

〔Example〕

The present invention will be specifically explained below using Examples. The compounds shown in Table 1 were used as the dispersion stabilizer of this invention. Parts and percentages in the examples are by weight.

Example 1 40 parts of quinacridone, which is an organic pigment, 60 parts of water, and 2 parts of a dispersion stabilizer were mixed as an organic powder in the proportions, and the mixture was mixed with a homogenizer at 200 rpm for 10 minutes to obtain an aqueous dispersion. Table 2 shows the test results of the dispersion stability and redispersibility of these dispersions in water.

<Dispersion stability> After preparing the aqueous dispersion, immediately place it in a 50 mfl graduated emulsification test tube, leave it in a constant temperature room at 25°C, observe the dispersion state of the quinacridone powder after 24 hours, and observe the following. It was evaluated as follows.

◎: No sedimentation at all.

O: Slight sedimentation.

△: Significant sedimentation.

×: Completely settled.

<Redispersibility> After preparing the dispersion in water, immediately put it into an emulsification test tube with a 50mα scale, leave it in a constant temperature room at 25°C, and check the hardness and redispersibility of the sediment after 30 days. It was evaluated as follows.

◎: Well dispersed.

○: Disperses when water is stirred.

△: Soft and easily crumbles when poked with a spatula ×: Hard and does not crumble easily when poked with a spatula Example 2 In a ratio of 60 parts of low-density polyethylene fine particles as an organic powder, 40 parts of water, and 2 parts of a dispersion stabilizer. The mixture was mixed and the same test as in Example 1 was conducted. Table 3 shows the dispersion stability and redispersibility of these dispersions in water.

]9 Example 3 Perylene, an organic pigment, was used as an organic powder to be dispersed in oil. Take 200g of perylene in a 2Q beaker,
4. Toluene with 2% dispersion stabilizer dissolved therein. OOg
was added and stirred for 3 minutes at 12 rpm using a 4-blade impeller.The mixture was allowed to stand for 3 minutes, and the wettability for luene was evaluated based on the remaining state of perylene at the bottom of the beaker on a scale of 1 to 4.

◎: All the powder is dispersed in the oil and does not remain at the bottom at all.

○: Most of the powder is dispersed in the oil, but a small amount remains at the bottom.

Δ: Approximately half of the powder remains at the bottom.

×: Most of the powder remains at the bottom.

Next, for those with a rating of 6 or higher, a
After stirring vigorously for 5 minutes with
A glass bar weighing 50 g was dropped into the dispersion through a guide provided at the top of the cylinder, and the sedimentation state was observed to evaluate the dispersion stability on two levels.

O: The rod reaches the bottom of the cylinder.

×: The rod stops without reaching the bottom of the cylinder, and a compacted layer is generated.

The results of these tests are shown in Table 4.

Table Example 4 Zinc stearate, a metal soap, was used as an organic powder to be dispersed in oil. A test similar to that in Example 3 was conducted by placing 300 g of zinc stearate in a 2Q beaker and adding 400 g of l-luene in which 2% of the dispersion stabilizer had been dissolved. The results are shown in Table 5.

Claims (1)

[Claims] 1. An organic powder comprising a copolymer of (a) a polyoxyalkylene derivative represented by formula (1) and (b) maleic anhydride, maleic acid, maleate or maleic acid ester. Dispersion stabilizer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (However, Z is the residue of a compound with 2 to 8 hydroxyl groups,
AO is an oxyalkylene group having 2 to 18 carbon atoms, R^1 is an unsaturated hydrocarbon group having 2 to 5 carbon atoms, and R^2 is an oxyalkylene group having 1 to 18 carbon atoms.
40 hydrocarbon groups or acyl groups, a=0-1000,
b=0~1000, c=0~1000, al+bm+c
n=1-3000, l=1-8, m=0-2, n=0-
7, l+m+n=2 to 8, m/(l+n)≦1/3. )